Condensed species in Titan's stratosphere: Confirmation of crystalline cyanoacetylene (HC3N) and evidence for crystalline acetylene (C2H2) on Titan

Infrared spectra of crystalline HC₃N and C₂H₂ were investigated at several temperatures between 15 and 150 K. The characteristics of the 505 and 753 cm⁻¹ bands of HC₃N are in complete agreement with the emission spectral data on Titan obtained by the Voyager IRIS instrument, thus confirming the identification of crystalline HC₃N on Titan. A composite spectrum in the 720-800 cm⁻¹ region, with contributions from HC₃N and C₂H₂ in crystalline phases, reproduces the Voyager emission data in that region, thus providing a suggestion for the identification of crystalline C₂H₂ on Titan.     

Condensed species in Titan's atmosphere: Identification of crystalline propionitrile (C2H5CN, CH3CH2CN) based on laboratory infrared data

We report the results of infrared studies of crystalline C₂H₅CN at several temperatures between 15 and 160 K. A case is made for the identification of crystalline C₂H₅CN in the stratosphere from the Voyager IRIS spectrum of Titan.     

Infrared spectroscopy of crystalline and amorphous diacetylene (C4H2) and implications for Titan's atmospheric composition

New laboratory spectra of crystalline and amorphous diacetylene ice have been recorded in the range of 7000-500 cm⁻¹ (1.4-20 μm) to aid in the identification of solid diacetylene on Saturn's moon Titan. We have established that amorphous diacetylene ice is stable only at temperatures less than 70±1 K. With respect to observations on Titan, the best approach would be to utilize future space-based telescopes to search for the ν₄ (3277/3271 cm⁻¹) in absorption against the reflected light from the sun and the slightly weaker ν₈ absorption bands (676/661 cm⁻¹) in absorption against the continuum emission.     

Influence of plasma on formation of crystalline Fe2SiO4 grains

The production of Fe₂SiO₄ (fayalite) crystalline grains was performed by two processes, namely, grain formation in a plasma field by evaporating a mixture powder of Fe and SiO and heat treatment of the product collected on the radio-frequency (RF) electrode side. Fe grains <20 nm in size covered with an amorphous SiO layer selectively formed Fe₂SiO₄ grains by heating at 800 °C. By heating at 600 °C, in addition to the formation of Fe₂SiO₄ crystal grains, the FeO phase appeared. The doping effect of excited oxygen in a plasma field into the Fe small grains may be the trigger on the formation of fayalite through the FeO phase formation. The present experimental result suggests that the probability of Fe₂SiO₄ grain formation in space is low.     

2–16 μm spectroscopy of micron-sized enstatite (Mg,Fe)2Si2O6 silicates from primitive chondritic meteorites

We present mid-infrared spectra from individual enstatite silicate grains separated from primitive type 3 chondritic meteorites. The 2–16 μm transmission spectra were taken with microspectroscopic Fourier-transform infrared (FT-IR) techniques as part of a project to produce a data base of infrared spectra from minerals of primitive meteorites for comparison with astronomical spectra. In general, the wavelength of enstatite bands increases with the proportion of Fe. However, the wavelengths of the strong En₁₀₀ bands at 10.67 and 11.67 decrease with increasing Fe content. The 11.67-μm band exhibits the largest compositional wavelength shift (twice as large as any other). Our fits of the linear dependence of the pyroxene peaks indicate that crystalline silicate peaks in the 10-μm spectra of Herbig AeBe stars, HD 179218 and 104237, are matched by pyroxenes of En₉₀₋₉₂ and En₇₈₋₈₀, respectively. If these simplistic comparisons with the astronomical grains are correct, then the enstatite pyroxenes seen in these environments are more Fe-rich than are the forsterite (Fo₁₀₀) grains identified in the far-infrared which are found to be Mg end-member grains. This differs from the general composition of type 3 chondritic meteoritic grains in which the pyroxenes are more Mg-rich than are the olivines from the same meteorite.     

Sulfurous acid (H2SO3) on Io?

Sulfurous acid (H₂SO₃) has never been characterized or isolated on Earth. This is caused by the unfavorable conditions for H₂SO₃ within Earth's atmosphere due to the high temperatures, the high water content and the oxidizing environment. Kinetic investigations by means of transition state theory showed that the half-life of H₂SO₃ at 300 K is 1 day but at 100 K it is increased to 2.7 billion years. Natural conditions to form H₂SO₃ presumably require cryogenic SO₂ or SO₂/H₂O mixtures and high energy proton irradiation at temperatures around 100 K. Such conditions can be found on the Jupiter moons Io and Europa. Therefore, we calculated IR-spectra of H₂SO₃ which we compared with Galileo's spectra of Io and Europa. From the available data we surmise that H₂SO₃ is present on Io and probably but to a smaller extent on Europa.     

The structure, ordering and equation of state of ammonia dihydrate (nh3 · 2h2o)

We present the first ab initio simulations of the low-pressure phase of ammonia dihydrate (NH₃ · 2H₂O), ADH I, a likely constituent of many volatile-rich solid bodies in the outer Solar System (e.g., Saturn’s moons). Ordered monoclinic (space group P2₁) and orthorhombic (space group P2₁2₁2₁) variants of the experimentally observed cubic cell (space group P2₁3) may be constructed, with fully ordered water molecule orientations that obey the ice rules. Our calculations show that the most stable structure at 0 K is orthorhombic (P2₁2₁2₁), the monoclinic variants (P2₁) being energetically disfavored. We provisionally call this ordered orthorhombic phase ADH III. The, as-yet-unmeasured, bulk modulus, K₀, is predicted to be 10.67−0.44+0.56 GPa at 0 K. Our results are also combined with literature data to arrive at a revised coefficient of volume thermal expansion, α_v = 2.81 × 10⁻⁷ T^1.39 (from 0-176 K), with the density at 0 K, ρ₀ = 991.7(39) kg m⁻³. We also present a case, based on literature data, that argues for a gradual transformation from a paraelectrically disordered cubic structure (P2₁3) to the proposed antiferroelectrically ordered orthorhombic structure (P2₁2₁2₁) around 130-150 K (cf. ice III → IX), a temperature regime that applies to the surfaces and interiors of many medium-sized (radii ∼500-700 km) icy bodies.     

Mercury: Absence of crystalline Fe2+ in the regolith

Reflectance spectra of terrain on Mercury containing both smooth plains and intercrater plains were obtained using a charge-coupled device spectrograph on 24 November 1984. The composite spectrum covers the 0.53- to 1.02-μm spectral range with a resolution of 17 Å. Absorption features due to telluric H₂O absorption are clearly mapped around 0.73, 0.82, and 0.93 μm. No evidence exists in the new spectrum for the proposed orthopyroxene absorption centered near 0.9 μm seen in older spectra of this terrain. The surface material is probably highly reduced, with any iron present in metallic form. Based upon the new spectrum, a history of heavy micrometeoroid bombardment of the Mercurian surface is suggested, resulting in a surface regolith primarily comprised of agglutinates.     

Seasonal variation of Titan's stratospheric ethylene (C2H4) observed

All previous observations of seasonal change on Titan have been of physical phenomena such as clouds and haze. We present here the first observational evidence of chemical change in Titan's atmosphere. Images taken during 1999-2002 (late southern spring on Titan) with the W.M. Keck I 10-meter telescope at 8-13 μm show a significant accumulation of ethylene (C₂H₄) in the south polar stratosphere as well as north-south stratospheric temperature variation (colder at poles). Our observations restrict this newly discovered south polar ethylene accumulation to latitudes south of 60° S. The only other observations of the spatial distribution of C₂H₄ were those of Voyager I, which found a significant north polar accumulation in early northern spring. We see no build-up in the north, although the highest northern latitudes are obstructed from view in the current season. Our observations constrain any unobserved north polar accumulation of C₂H₄ to north of 50° N latitude. Comparison of the Voyager I results with our new results show seasonal chemical change has occurred in Titan's atmosphere.     

Auroral N2(c′4Σu → aΠg emission

Inspection of recent spectra presented by Sivjee (1983) show evidence of the 0–4 and 0–5 bands of the N₂(c′₄¹Σ_u⁺ → a¹Π_g) Gaydon-Herman system. In conjunction with earlier spectra, it is now possible that this band system is a significant auroral component, with an intensity approx. 7% that of the N2 2P system. The absence in aurorae of the potentially far stronger N₂(c′₄¹Σ_u⁺ → X¹Π_g) system is discussed. It is that the O₂(A³Σ_u⁺ → X³Σ_g⁻) band system is indiscernible in Sivjee's auroral spectra, under conditio the foreground nightglow is expected to be clearly visible. On the other hand, at least one relatively strong O₂(A′³Δ_u → a¹Δ_g) band appears to be present in these spectra.     

The excitation of O2(b1Σg+) in the nightglow

It is proposed that the available measurements of the O₂(b¹Σ_g⁺ ?X³Σ_g^?) atmospheric bands both in the nightglow and in the laboratory indicate that the excitation mechanism is a two-step process rather than the direct three body recombination of atomic oxygen. It is shown that such a two-step mechanism can explain observations of the atmospheric bands both in altitude and intensity.     

Improved Determination of Ethane (C2H6) Abundance in Titan's Stratosphere

Ethane spectral lines were observed in emission from Titan in August 1993, October 1995, and September 1996, at a spectral resolution of λ/Δλ≈10⁶, at wavelength 11.7−11.9 μm using the Goddard Infrared Heterodyne Spectrometer at the NASA Infrared Telescope Facility on Mauna Kea, Hawaii. The ethane mole fraction is determined to be (8.8±2.2)×10⁻⁶ (68.3% confidence limits, “1σ”), averaging the retrievals from each observing run obtained using the “recommended” thermal profile of R. V. Yelle, D. Strobel, E. Lellouch, and D. Gautier (1997, in Huygens: Science, Payload, and Mission (J.-P. Lebreton, Ed.), pp. 243-256, European Space Agency SP-1177).     

EUV resonance fluorescence of the c′4→X (0,v″) and b′→X (1,v″) transitions of N2

Extreme ultraviolet (EUV) resonance fluorescence of the (0,v″) bands of the c′₄¹Σ_u⁺→X¹Σ_g⁺ and the (1,v″) bands of the b′ ¹Σ_u⁺→X¹Σ_g⁺ transitions of N₂ has been observed by photon excitation of N₂ in the vicinity of 95.8 nm. The integrated fluorescence intensities of the c′₄→X (0,v″) emission become saturated at N₂ pressures higher than ∼0.16 mTorr. The emission features in the spectral region between 105 and 130 nm become progressively significant as the N₂ pressure is increased. The (1,v″) progression for v″ up to 11 of the b′→X transition and two progressions of the Lyman-Birge-Hopfield (LBH) system have been identified. The multiple scattering processes apparently cause significant reduction in the c′₄→X (0,0) emission rates. The present results may be useful in the explanation of the weak c′₄→X (0,0) fluorescence as well as the significant c′₄→X (0,v″) features in the dayglow of the Earth observed by the Far Ultraviolet Spectroscopic Explorer.     

Quenching of O+(2D) by electrons in the thermosphere

A major loss process for the metastable species, O⁺(²D), in the thermosphere is quenching by electrons

$\text{O}{}^{\mathrm{+}}\text{(}{}^2\text{D) + e → O}{}^{\mathrm{+}}\text{(}{}^4\text{S) + e}$

.To date no laboratory measurement exists for the rate coefficient of this reaction. Thermospheric models involving this process have thus depended on a theoretically calculated value for the rate coefficient and its variation with electron temperature. Earlier studies of the O⁺(²D) ion based on the Atmosphere Explorer data gathered near solar minimum, could not quantify this process. However, Atmosphere Explorer measurements made during 1978 exhibit electron densities that are significantly enhanced over those occurring in 1974, due to the large increases that have occurred in the solar extreme ultraviolet flux. Under such conditions, for altitudes ? 280 km, the electron quenching process becomes the major loss mechanism for O⁺(²D), and the chemistry of the N⁺₂ ion, from which the O⁺(²D) density is deduced, simplifies to well determined processes. We are thus able to use the in situ satellite measurements made during 1978 to derive the electron quenching rate coefficient. The results confirm the absolute magnitude of the theoretical calculation of the rate coefficient, given by the analytical expression k(T_e) = 7.8 × 10^?8 (T_e/300)^?0.5cm³s^?1. There is an indication of a stronger temperature dependence, but the agreement is within the error of measurement.     

An experimental study of the reaction kinetics of C2(XΣg) with hydrocarbons (CH4, C2H2, C2H4, C2H6 and C3H8) over the temperature range 24-300 K: Implications for the atmospheres of Titan and the Giant Planets

The reactivity of C₂(X¹Σ⁺_g) with simple saturated (CH₄, C₂H₆ and C₃H₈) and unsaturated (C₂H₂ and C₂H₄) hydrocarbons has been studied in the gas phase over the temperature range 24-300 K using the CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme or Reaction Kinetics in a Uniform Supersonic Flow) technique. All reactions have been found to be very rapid in this temperature range and the rate coefficients are typically ?10⁻¹⁰ cm³ molecule⁻¹ s⁻¹ with the exception of methane for which the rate coefficient is one order of magnitude lower: ∼10⁻¹¹ cm³ molecule⁻¹ s⁻¹. These results have been analyzed in terms of potential destruction sources of C₂(X¹Σ⁺_g) in the atmospheres of Titan and the Giant Planets. It appears that the rate coefficient of the reaction ¹C₂ + CH₄ should be updated with our new data and that reactions with C₂H₂, C₂H₄ and C₂H₆ should also be included in the existing photochemical models.     

Laboratory investigation of the ionospheric O2+(X2πg, v ≠ 0) reaction with NO

Laboratory measurements of the reaction of O₂⁺ with NO from thermal energy to 0.6 eV in an Ar buffered flow drift tube agree with similar measurements made earlier in the same drift tube with He buffer. Since the O₂⁺ ions are substantially vibrationally excited in Ar and not in He it follows that the reaction is not enhanced by vibrational excitation of the O₂⁺.     

Changes in thermospheric composition inferred from twilight O+(2P) emission

Measurements of the twilight enhancement of airglow emission from O⁺(²P) near 7325 Å reveal major changes which accompany geomagnetic activity, no significant distance between evening and morning and an increase in brightness paralleling the approach to solar maximum. The principal source for O⁺(²P) is direct photoionization from O(³P) but at low solar activity there appears to be a contribution from another source in early twilight which may be local photoelectron ionization into O⁺(²P). The geomagnetic and solar effects appear to reflect changes in the O and N₂ density in the thermosphere; ground based twilight measurements of O⁺ emissions thus provide a simple means for monitoring thermospheric structure from 300 km to ～ 500 km at solar minimum and to ～600 km at solar maximum.     

Associative ionization of N(2D) and O

Recent laboratory measurements have shown that N(²P) atoms, and thus probably hot N(²D) atoms, will recombine with atomic oxygen via an associative ionization process at the gas kinetic rate. While the reaction is endothermic, it has been suggested that this has interesting implications for the upper atmosphere in that N(²D) atoms in the tail of the velocity distribution could provide an additional source of NO⁺ through the reverse of the dissociative recombination reaction

$\text{NO}{}^{\mathrm{+}}\text{+ e ?}\text{N}\text{(}{}^2\text{D}\text{) +}\text{O}$

. It has also been suggested that this process might account for the difference between a laboratory determination of the rate coefficient and that determined from the Atmospheric Explorer Satellite data. In this paper we investigate further the likelihood of the associative ionization of N(²D) and O playing a significant role in the normal ionosphere, in the light of several recent relevant studies. We conclude that the associative ionization process is not an important factor and that a more probable cause for disagreements in the various determinations of the recombination coefficient, is the difference in excited states of the ions in the various experiments.